Process of printing fabrics with aryl sulfonhydrazides



Patented Apr. 22, 1952 PROCESS OF PRINTING FABRICS WITH ARYL SULFONHYDRAZIDES Joseph A. Sprung and Willy A. Schmidt, Easton,

Pa., assignors to General Aniline & Film Corporation, New York, N. Y.,- a corporation of Delaware I j No Drawing.

This invention relates to the manufacture of. insoluble azo dyestuffs and in particular on the fiber and to the process by which such insoluble azo dyestuiisare printed and developedon-the fiber.

The problem of developing ,azo colors in situ on fabrics and the methods .of producing printed designs on textiles havebeen the subject of considerable study. The earlier attempts 'to develop azo colors on the fabrics were made by padding an alkaline solution of Z-naphthol on to the cloth and then treatin -this with'a diazotized amine. As many amines are unstable when warm, ice had to be added to the diazo solutions to prevent their decomposition, hence this type of color produced from'the reaction of'the di'azotized amine and the. padded coupling component became knownlas an" ice color. a V

Since the'use of ice was obviously undesirable; methods of improvement were sought. It was laterdiscovered that certain compounds such as" Application September 20. 1951, Serial No. 247,551

c ai s. (01.. 8-415 has the; disadvantage that the fumes necessary forthe development of the color are very corrosive and hence undesirable. It is obvious, therefore, that any method of. developing azo dyes: on the fabric under neutral conditions or in the absence of corrosive acid fumes would be most desirable.

Accordingly this invention has for its object the provision of preparations which are stable under practical conditions pending and during their application to fabrics from which insoluble azo colors maybe developed under neutral condi'tio'ns,such as air, and air and steam, without the use of acidfume's.

It-has been discovered, in the accomplishment of this object, that the 2-aryl sulfonhydrazides when applied in a print paste may be employed for the production of insoluble azo colors on fabzinc chloride, naphthalene. sulfonic acids,.fluoro-- boric acid and other agents which would form. salts of the .diazonium chloride'would produce stable products which would nevertheless couple with the naphthol coupling components. However, the strong coupling. tendency of these diazo nium salts precluded mixing them with couplers, and it was still necessary to pad the cloth witlithe" naphthol coupler. This. classof stabilized diazo components is known .as the Fast.ColorS al ,ts. Other compounds found to. be'u'sefullfor. the situ printing of fabrics with azo' colors are the nitrosamines which have gained onlyzlimited use due to the lack of brightness and instability of the colors.

A major step in the development of this art was made by the discovery that diazonium compounds reacted with certain secondary amines to give diazo amino ortriazene compounds which were quite stable, but could behydrolyzed under acidic conditions to the diazo compound. These diazoamino 0r triazene compounds may be mixed with the coupling component and the mixture printed" on the fabric. The color is then developed by ckposing the printed fabric to an acid condition, such as moist formic or acetic acid fumes, whereupon hydrolysis of the diazo amino compound and coupling of the diazo compound with the coupling component occurred simultaneously. This method of azo dye printing in situ on the fabric has en joyed extended use for a number of years, but

rics by a process involving oxidation by air, and steam and air of the aryl sulfonhydrazides in the presence of the coupling component. These aryl sulfonhydrazides may be represented by the formula; I

ANH-NHSO2R I V wherein A is an aryl radical such as phenyl,

I naphthyl, biphenyl and bis-biphenyl and R represents an alkyl or aryl radical.

The aryl sulfonhydralzides may be applied to the fabric and the color developed by one of two methods.

1. The fabric is first impregnated with a solution of the coupling component such as a, naphthol 5 derivativema'pable"pf fi f the coupling function. i The sulfonhydrazide is then made into apaste and is printed on the thus impregnated fabric. The azo dye color is then developed by immersing the printed fabric into a solutioncontainingmild oxidizing agents and coupling acchamber (cottage aging).

oelerants or lay-introducing it into an tmosphere of'oXygen-or air, air and steam (vat aging), or air and steam under pressure in a vat aging 2. The sulfonhydrazide, the coupling component and a stabilizing agent may be made into a paste and printed onthe textile fabric. The de velopment of the azo dye print is then carried out by one of the methods recited above. In preparing the paste of the sulfonhydrazide and the coupling component sodium sulfite'or sodium hydrosulfite,- for example, may be usedas stabilizing a ents.

- ;'I'he oxidizing agents, i. e. oxygen, air, air and steam; arepa'rticu'larly useful for the develop- 3 ment of azo dyes wherein the coupling component is impregnated into the fabric and this is overprinted by a paste containing the sulfonhydrazide. A typical paste of the sulfonhydrazide which is adapted for printing on cotton and acetate would contain 0.25 g. of the sulfonhydrazide. 4 cc. dimethyl formamide.

4 cc. of water.

22 g. starch tragacanth.

The immersion time in the developing or oxidizing solution is approximately twenty minutes.

The invention is more fully and specifically illustrated by the following examples:

Example .1

A solution of .25 g. ,fi-(i-acetamidophenylibenzenesulfonhydrazide in 4 cc. dimethylformamide was poured into a mixture of 4 cc. water and 22g. starch tragecanth. The resulting paste was'screen printed on textile fabrics which had been impregnated with the'sodium salt of naphthyl amide derivative of 2,3-hydroxy naphthoic acid.

The red azo dye print was developed, by intros ducing the fabric into a chamber containing steam and oxygen for a period of ten to twenty minutes. I

Example 2 A solution of 0.2 g. p-( i-acetamidophenybbenzenesulfonhydrazide in 4 cc. dimethyl formamide was thoroughly mixed into a paste with 0.15 g. of the naphthyl amide derivative of 2,3-hydroxy naphthoic acid on x11. 3 (o Example 3 s (4 aoetamidophenyl) benzenesuifonhydrazide A solution of 15.2 g. (0.05 mole) of 4-acetamis dobenzenediazo-(phenyl)-sulfone in 100 cc. dimethyl formamide, 5.8 cc. glacial acetic acid and 5 cc. water Was slowly treated with zinc dust until the color of the solution had changed from a deep orange to a faint yellow. The temperature was not allowed to rise above 40 C. The zinc salts were removed by filtration and the filtrate was poured into a cold solution of 10 cc. concentrated hydrochloric acid in 1000 cc. water. The sulfonhydrazide, which precipitated, was removed by filtration, washed well with water and air dried. Yield==11.4 g. (74%).

Example 4 s (Phenyl) -3-carboxybenzenesulfonhydrazide coon To a solution of 43.0 g. (0.4: mole) phenylhydrazine in 250 cc. ether was slowly added (ice bath) with stirring, 44.3 g. (0.2 mole) 3-chlorosulionyl benzoic acid in 250 cc. of ether. After the mixture had remained at room temperature for 1 hour,-250 cc. of low boiling petroleum ether was added,- and the solid material was removed by filtration and washed with petroleum ether. The product was digested with 1 liter dilute hydrochloric acid to remove the phenylhydrazine hydrochloride, and the residue was recrystallized from dilute ethanol. Yield=44.0 g. (75%) M. P. 178 C. with decomposition.

Example 5 e (2 ethoxyphenyl) methanesulfonhydra- A mixture of 37.0 g. (0.2 mole) of 2-ethoxyphenylhydrazine hydrochloride, 22.9 g. (0.2 mole) methane suifonyl chloride and 33.6 g. (0.4 mole) sodium bicarbonate in 400 cc. ethyl ether was stirred for 1 hour at room temperature and finally refluxed for 2 hours on a steam bath. The cooledmixture was treated with 400 cc. low boiling petroleum ether, and the precipitated material was removed by filtration and was washed with petroleum ether. The solid was digested twice at room temperature with dilute hydrochloric acid (5 cc. hydrochloric acid in 250 cc. water), and was finally washed with water and air dried- Yield=o g- (87%) P C- Ecample 6 p (2,4-dimethy1-5-benzamidophenyl) i-acetamidobenzenesulfonhydrazide NHCOCaHa A solution of 3.0 g. (0.00665 mole) of 2,4-dimethyl-5-ibenzamidodiazo(4 acetamidophenyl) sulione in 25 cc. of dimethyl formamide and 2 cc. glacial acetic acid was treated with Zinc dust until the color of the solution had changed from a deep orange to a faint yellow. Th zinc salts were removed by filtration, and the filtrate was poured into 100 cc. water. The sulfonhydrazide wasv removed by filtration, washed, first with Water, finally with 50% ethanol and was dried in a vacuum desiccator over phosphorus pentoxide. Yield=2.8 g. (93%) M. P. with decomposition.

E e 7 .3 542,4 dimethyl-5-benzamidophenyl) 4-08- sulfoethoxy) benzenesulfonhydrazide (sodium salt) on NHNHSOe-0CHg-CHz-SOiNa- NHCOCaHs A solution of 2.1 g. (0.0039 mole) of 2,4-dimethyl 5 benzamidobenzenediazol4 (Bsulfoethoxy)-phenyl]-sulfone in 20 cc. of dimethylformamide and 1 cc. glacial acetic acid was treated with sufficient zinc dust to cause the color of the solution to change from an orange to a faint yellow. The zinc salts were removed by filtration, and the filtrate was diluted with 75 cc. acetone and 100 cc. of low boiling ether. The sulfonhydrazide was removed by filtration and was air dried. Yield=1.7 g. (81%).

Example 8 B 8 Di(4-acetamidobenzenesulfonyl) 3,3 dimethoxy-4,4'-biphenylene dihydrazine OCH:

A solution of 5.0 g. (0.0075 mole) of 3,3'dimethoxy 4,4-biphenyl-bis-diazo(4 acetamidophenyDdisulfone in 35 cc. dimethyl formamide and 2 cc. glacial acetic acid was reduced in the usual manner with zinc dust. The zinc salts were removed by filtration and the filtrate was poured into 100 cc. water. The sulfonhydrazide was removed by filtration, washed well with water and dried in a vacuum desiccator over phosphorus pentoxide. Yield=4.1 g. (82%).

Ear-ample 9 as Di[4 -03"-sulfoethoxy)benzenesulfonyl]- 3,3-dimethoxy-4,4'-biphenylenedihydrazine (disodium salt) OCH:

A solution of 2.1 g. (0.0025 mole) of 3,3'-dimethoxy-4,4'-biphenylene-bis-diazo[4 (c-sulfoethoxy)-phenyl]-disulfone in 2 cc. water, 1 cc. acetic acid and 25 cc. of dimethyl formamide was treated with zinc dust at room temperature until the color of the solution changed from 'a deep red to a faint orange. The zinc compounds were removed by filtration, and the filtrate was poured into 150 cc. of cold acetone. The bissulfonhydrazide, which separated, was removed by filtration and washed with acetone. Yield=1.3 g. (62%).

Any coupling component which can be impregnated into the fiber which it is desired to print or which can be incorporated into the printing paste with the sulfonhydrazide to produce the desired color may be employed in place of the naphthylamide of 2,3-hydroxy naphthoic acid used in Examples 1 and 2. The following are typical of such coupling components:

1. The anilide of 2,3-hydroxy naphthoic acid having the formula- .6, 2; 2,5-dimethoxy anilide of 2,-3-hydrox'y naphthoic acid having the formular l OCH:

3. The o-toluidide of 2-hydroxy anthracene-B- carboxylic acid CKIJ' 'U Various modifications of our invention will occur to persons skilled in the art and, therefore, we do not intend to be limited in the patent granted except as required by the prior art and the appended claims.

This application is a continuation-in-part of our application Serial Number 66,566, filed December 21, 1948, now abandoned.

We claim:

1. A process of printing and dyeing textile fabrics by developing azo dyes on the fabric which comprises padding the textile fabric with a composition containing a coupling component, printing over with a 2-aryl sulfonhydrazide dissolved in a print paste, and introducing the padded textile fabric into an atmosphere selected from the class consisting of air:;and steam and air.

2. A process of printing and dyeing textile fabrics by developing azo dyes on the fabric, which comprises paddingithe textile fabric with a composition containing an arylamide of 2,3- hydroxynaphthoic acid, printing over with a 2- aryl sulfonhydrazide dissolved in a print paste, and introducing the padded textile fabric into an atmosphere selected from the class consisting of air and steam and air. I

3. A process of printing and dyeing textile fabrics by developing azo dyes on the fabric, which comprises padding the textile fabric with a composition containing an arylamide of 2,3- hydroxynaphthoic acid, printing over with a 2- aryl sulfonhydrazide dissolved in a print paste, and introducing the padded textile fabric into air.

4. A process of printing and dyeing textile fabrics by developing azo dyes on the fabric which comprises padding the textile fabric with a composition containing an arylamide of 2,3-hydroxy naphthoic acid, printing over with a 2-ary1 sulfonhydrazide dissolved in a print paste and introducing the padded textile fabric into an atmosphere of steam and oxygen.

7 5, A process of printing and dyeing textile fabrics by developing azo dyes on the fabric; which comprises padding the textile fabric with a composition containing an arylamide of 2,3- hydroxynaphthoic acid, printing over with a 2- aryl sulfonhydrazide dissolved in a print paste, and introducing the padded textile fabric into an atmosphere of oxygen.

JOSEPH A. SPRUNG.

WILLY A. SCHMIDT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,078,861 Lantz Apr. 27, 1937 2,424,256 Schmidt Ju1y'22, 194? 

1. A PROCESS OF PRINTING AND DYEING TEXTILE FABRICS BY DEVELOPING AZO DYES ON THE FABRIC WHICH COMPRISES PADDING THE TEXTILE FABRIC WITH A COMPOSITION CONTAINING A COUPLING COMPONENT, PRINTING OVER WTIH A 2-ARYL SULFONHYDRAZIDE DISSOLVED IN A PRINT PASTE, AND INTRODUCING THE PADDED TEXTILE FARBIC INTO AN ATMOSPHERE SELECTED FROM THE CLASS CONSISTING OF AIR AND STEAM AND AIR. 